Kinetic evolution studies of silver nanoparticles in a bio-based green synthesis process

Silver nanoparticles are being extensively studied due to their widespread applications and unique properties. In the present study, the growth kinetics of silver nanoparticles as synthesized on reduction of silver nitrate solution by aqueous extract of Azadirachta indica leaves was investigated. The formation of silver nanoparticles was preliminarily monitored by measuring the absorption maxima at different time intervals after adding the reducing agent to the silver salt solution (0.5, 1, 1.5, 2, 2.5, 3, 3.5 and 4 h). At different time points characterization studies were conducted using X-ray diffraction studies, FT-IR techniques, zeta potential studies and transmission electron microscopy. The total available silver in the reaction medium was determined at different durations using ICP-OES. The changes in reduction potential in the medium were also monitored using potentiometric analysis. The results confirm a definite change in the medium pertaining to formation of the stable nanoparticles after 2 h, and a significant increase in the agglomeration tendency after 4 h of interaction. The growth kinetic data of the nanoparticles till 3.5 h was found to fit the LSW model confirming diffusion limited growth. (C) 2011 Elsevier B.V. All rights reserved.

Metal-insulator transitions in metal clusters: a high-energy spectroscopy study of palladium and silver clusters

Bremsstrahlung isochromat spectroscopy (BIS) along with ultraviolet and X-ray photoelectron spectroscopy (UPS and XPS) has been employed to investigate the electron states of Pd and Ag deposited on amorphous graphite at different coverages. The metal core level binding energies increase with decreasing cluster size while the UPS valence bands show a decrease in the 4d states at E(F) accompanied by a shift in the intensity maximum to higher binding energies. BIS measurements show the emergence of new states closer to E(F) with increase in the cluster size. It is pointed out that the observed spectral shifts cannot be accounted for by final-state effects alone and that initial-state effects have a significant role. It therefore appears that a decrease in cluster size is accompanied by a metal-insulator transition.

A facile route to synthesize silver nanoparticles in polyelectrolyte capsules

We are reporting a novel green approach to incorporate silver nanoparticles (NPs) selectively in the polyelectrolyte capsule shell for remote opening of polyelectrolyte capsules. This approach involves in situ reduction of silver nitrate to silver NPs using PEG as a reducing agent (polyol reduction method). These nanostructured capsules were prepared via layer by layer (LbL) assembly of poly(allylamine hydrochloride) (PAH) and dextran sulfate (DS) on silica template followed by the synthesis of silver NPs and subsequently the dissolution of the silica core. The size of silver nanoparticles synthesized was 60 +/- 20 nm which increased to 100 +/- 20 nm when the concentration of AgNO3 increased from 25 mM to 50 mM. The incorporated silver NPs induced rupture and deformation of the capsules under laser irradiation. This method has advantages over other conventional methods involving chemical agents that are associated with cytotoxicity in biological applications such as drug delivery and catalysis. (C) 2011 Elsevier B.V. All rights reserved.

Representation of thermodynamic properties of ternary systems and its application to the system silver-gold-copper at 1350 K

The article presents a generalized analytical expression for description of the integral excess Gibbs free energy of mixing of a ternary system. Twelve constants of the equation are assessed by the least mean squares regressional analysis of the experimental integral excess data of the constituent binaries; three ternary parameters are evaluated by a regressional analysis based on the partial experimental data of a component of the ternary system. The assessed values of the ternary parameters describe the nature of the ternary interaction in the system. Activities and isoactivities of the components in the Ag-Au-Cu system at 1350 K are calculated and found to be in good agreement with the experimental data. This analytical treatment is particularly useful to ternary systems where the thermodynamic data are available from different sources.

Symmetrizing a Hessenberg matrix: Designs for VLSI parallel processor arrays

A symmetrizer of a nonsymmetric matrix A is the symmetric matrix X that satisfies the equation XA = A(t)X, where t indicates the transpose. A symmetrizer is useful in converting a nonsymmetric eigenvalue problem into a symmetric one which is relatively easy to solve and finds applications in stability problems in control theory and in the study of general matrices. Three designs based on VLSI parallel processor arrays are presented to compute a symmetrizer of a lower Hessenberg matrix. Their scope is discussed. The first one is the Leiserson systolic design while the remaining two, viz., the double pipe design and the fitted diagonal design are the derived versions of the first design with improved performance.

Effect of substrate on particle arrangement in arrays formed by self-assembly of polymer grafted nanoparticles

We show that the substrate affects the interparticle spacing in monolayer arrays with hexagonal order formed by self-assembly of polymer grafted nanoparticles. Remarkably, arrays with square packing were formed due to convective shearing at a liquid surface induced by miscibility of colloidal solution with the substrate.

Degradation and Failure of Field Emitting Carbon Nanotube Arrays

It has been observed experimentally that the collective field emission from an array of Carbon Nanotubes (CNTs) exhibits fluctuation and degradation, and produces thermal spikes, resulting in electro-mechanical fatigue and failure of CNTs. Based on a new coupled multiphysics model incorporating the electron-phonon transport and thermo-electrically activated breakdown, a novel method for estimating accurately the lifetime of CNT arrays has been developed in this paper. The main results are discussed for CNT arrays during the field emission process. It is shown that the time-to-failure of CNT arrays increases with the decrease in the angle of tip orientation. This observation has important ramifications for such areas as biomedical X-ray devices using patterned films of CNTs.

Monte Carlo simulation of ion conduction in silver based glassy electrolytes

A simplified structural model to study the ionic transport in silver based glasses has been formulated. The diffusion of silver ion under the influence of coulombic interactions of mobile cation and anions has been studied. Monte Carlo simulations of silver ion hopping in glass have suggested two different kinds of population of silver ions. We discuss the results of variation in diffusion constant with dopant (AgI) concentration using the diffusion path model. (C) 1997 Elsevier-Science S.A.

Role of silver doping in oxygen incorporation of oxide thin film

A distinctive characteristic of silver in oxygen incorporation of oxide thin films during pulsed laser ablation has been discovered. Optical emission spectroscopy studies of laser-induced plume of Ag-target indicates the presence of AgO species whose concentration increases with an increase in oxygen partial pressure. The formation of AgO in laser-plume has been found to be very useful for the realization of high temperature superconducting YBa2Cu3O7-delta (YBCO) and giant magnetoresistive La0.7MnO3-delta (LMO) thin films with dramatically superior quality if the target materials contained a small amount of silver. The improvement in the quality of these films is brought about by the supply of atomic oxygen to oxide lattices during their formation. This becomes possible due to the fact that Ag, after it is ablated with other constituent materials in the target, gets moderately oxidized in an oxygen atmosphere and the oxidized species dissociate back into Ag and nascent O at the substrate surface. The nascent oxygen is very highly reactive and is easily assimilated into the lattice of these compounds. (C) 1997 Elsevier Science S.A.

Structure and silver ion transport in AgI-Ag2MoO4 glasses: A molecular dynamics study

The structure and dynamics of silver ion conducting AgI-Ag2MoO4 glasses have been simulated by molecular dynamics simulation over a wide range of compositions. Formation of silver iodide like aggregates have been identified only in the AgI rich glasses. Increase in silver ion conductivity with an increase in AgI content in the glass is seen as in experiments. The dynamics of ion transport suggests that Ag+ ion transport occurs largely through paths connected by silver ion sites of mixed iodide-oxide coordination. The Van Hove correlation functions indicate that Ag+ ions prefer migration along the pathways formed with connected sites of similar coordination.

Self-assembled molecular films of tetraamino metal (Co, Cu, Fe) phthalocyanines on gold and silver. Electrochemical and spectroscopic characterization

The formation of molecular films of 2,9,16,23-tetraamino metal phthalocyanines [TAM(II)Pc; M (II) = Co, Cu, and TAM(III)Pc; M = Fe] by spontaneous adsorption on gold and silver surfaces is described. The properties of these films have been investigated by cyclic voltammetry, impedance, and FT-Raman spectroscopy. The charge associated with Co(II) and Co(I) redox couple in voltammetric data leads to a coverage of (0.35+/-0.05) x 10(-10) mol cm(-2), suggesting that the tetraamino cobalt phthalocyanine is adsorbed as a monolayer with an almost complete coverage. The blocking behavior of the films toward oxygen and Fe(CN)(6)(3-/4-) redox couple have been followed by cyclic voltammetry and impedance measurements. This leads to an estimate of the coverage of about 85 % in the case of copper and the iron analogs. FT-Raman studies show characteristic bands around 236 cm(-1) revealing the interaction between the metal substrate and the nitrogen of the -NH2 group on the phthalocyanine molecules.

Tailoring the microstructure and mechanical properties of arrays of aligned multiwall carbon nanotubes by utilizing different hydrogen concentrations during synthesis

We synthesize vertically aligned arrays of carbon nanotubes (CNTs) in a chemical vapor deposition system with floating catalyst, using different concentrations of hydrogen in the gas feedstock. We report the effect of different hydrogen concentrations on the microstructure and mechanical properties of the resulting material. We show that a lower hydrogen concentration during synthesis results in the growth of stiffer CNT arrays with higher average bulk density. A lower hydrogen concentration also leads to the synthesis of CNT arrays that can reach higher peak stress at maximum compressive strain, and dissipate a larger amount of energy during compression. The individual CNTs in the arrays synthesized with a lower hydrogen concentration have, on average, larger outer diameters (associated with the growth of CNTs with a larger number of walls), but present a less uniform diameter distribution. The overall heights of the arrays and their strain recovery after compression have been found to be independent of the hydrogen concentration during growth. (C) 2011 Elsevier Ltd. All rights reserved.

Role of spacer lengths of gemini surfactants in the synthesis of silver nanorods in micellar media

In this work, we have prepared Ag-nanorods using biscationic gemini surfactant micelles as the media by a seed-mediated wet synthesis method. Towards this end, we first synthesized Ag-nanoseeds of diameter similar to 7 nm stabilized by trisodium citrate (as the capping agent). Then these Ag-nanoseeds were used to synthesize Ag-nanorods of different aspect ratios. With decreasing Ag-nanoseed concentration, the aspect ratios of the Ag-nanorods stabilized by these gemini surfactants increased gradually. Various Ag-nanoseeds and Ag-nanospecies were characterized using UV-Vis spectroscopy (to know the surface plasmon bands), transmission electron microscopy (to find out their particle sizes and distribution), energy-dispersive X-ray spectroscopy and X-ray diffraction. When we used micelles derived from gemini surfactants of shorter spacer-(CH(2))(n)-(n = 2 or 4) to stabilize the Ag-nanorods, the lambda(max) of the longitudinal band shifted more towards the blue region compared to that of the gemini surfactant micelles with a longer spacer-(CH(2))(n)-(n = 5, 12) at a given amount of the Ag-nanoseed solution. So, the growth of Ag-nanorods in the gemini micellar solutions depends on the spacer-chain length of gemini surfactants employed.

A General Route to Nanoparticle Thin Films and Coatings

Nanoparticles thin films have wide range of applications such as nanoelectronics, magnetic storage devices, SERS substrate fabrication, optical grating and antireflective coating. Present work describes a method to prepare large area nanoparticles thin film of the order of few square centimeters. Thin film deposition has been done successfully on a wide range of conducting as well as non conducting substrates such as carbon-coated copper grid, silicon, m-plane of alumina, glass and (100) plane of NaCl single crystal. SEM, TEM and AFM studies have been done for microstructural characterization of the thin films. A basic mechanism has been proposed towards the understanding of the deposition process.

Tailoring of Structural Morphology of Silver Nanowires in Electrochemical Growth

Noble metal such as Ag normally exists in an fcc crystal structure. However as the size of the material is decreased to nanometer lengthscales, a structural transformation from that of its bulk state can be expected with new atomic arrangements due to competition between internal packing and minimization of surface energy. In many previous studies, it has been shown that silver nanowires (AGNWs) grown inside anodic alumina (AAO) templates by ac or dc electrochemical deposition from silver salts or complexes, adopt fcc structure and below some critical diameter ∼ 20 nm they may acquire hcp structure at low temperature. This is, however, critically dependant on the nature of confinement, as AgNWs grown inside nanotube confinement with subnanometer diameter have been reported to have fcc structure. Hence the question of the crystal structure of metal nanowires under combined influence of confinement, temperature and deposition condition remains open. In this abstract we show that the alternative crystal structures of AGNWs at room temperature can be achieved with electrochemical growth processes under specific conditions determined by the deposition parameters and nature of confinement. We fabricated AgNWs of 4H hexagonal structure with diameters 30 – 80 nm inside polycarbonate (PC) templates with a modified dc electrodeposition technique, where the nanowires were grown at deposition potentials as low as 10 mV in 2 M silver nitrate solution[1]. We call this low-potential electrodeposition (LPED) since the electrodeposition process occurs at potential much less than the standard Nernst potential (770 mV) of silver. Two types of electrodes were used – stainless steel and sputtered thin Pt film, neither of which had any influence on the crystal structure of the nanowires. EDS elemental analysis showed the nanowires to consist only of silver. Although the precise atomic dynamics during the LPED process is unclear at present, we investigated this with HRTEM (high-resolution transmission electron microscopy) characterization of nanowires grown over various deposition times, as well as electrical conductivity measurements. These experiments indicate that nanowire growth does not occur through a three-dimensional diffusion controlled process, as proposed for conventional over-potential deposition, but follow a novel instantaneous linear growth mechanism. Further experiments showed that, (a) conventional electrochemical growth at a small over-potential in a 2 mM AgNO3 solution yields nanowires with expected fcc structure inside the same PC templates, and (2) no nanowire was observed under the LPED conditions inside hard AAO templates, indicating that LPED-growth process, and hcp structure of the corresponding nanowires depend on deposition parameters, as well as nature of confinement.